WO2009081549A1 - Corps moulé composite - Google Patents

Corps moulé composite Download PDF

Info

Publication number
WO2009081549A1
WO2009081549A1 PCT/JP2008/003826 JP2008003826W WO2009081549A1 WO 2009081549 A1 WO2009081549 A1 WO 2009081549A1 JP 2008003826 W JP2008003826 W JP 2008003826W WO 2009081549 A1 WO2009081549 A1 WO 2009081549A1
Authority
WO
WIPO (PCT)
Prior art keywords
polybutylene terephthalate
terephthalate resin
composite molded
reinforcing agent
fibrous reinforcing
Prior art date
Application number
PCT/JP2008/003826
Other languages
English (en)
Japanese (ja)
Inventor
Yasumitsu Miyamoto
Nobuyuki Matsunaga
Original Assignee
Wintech Polymer Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wintech Polymer Ltd. filed Critical Wintech Polymer Ltd.
Priority to US12/746,617 priority Critical patent/US20100261025A1/en
Priority to CN2008801215376A priority patent/CN101903170A/zh
Publication of WO2009081549A1 publication Critical patent/WO2009081549A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/016—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10779—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyester
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Definitions

  • the present invention relates to a composite molded body made of a metal and a polybutylene terephthalate resin material.
  • Polybutylene terephthalate resin has excellent mechanical properties, electrical properties, heat resistance and chemical resistance, so it is widely used as an engineering plastic for various applications such as automotive parts, electrical / electronic components, etc.
  • Composite molded bodies produced by insert or outsert molding of butylene terephthalate resin and metal are also used.
  • In order to manufacture such a composite molded body of resin and metal as a technique for bringing the resin into close contact with the metal surface, studies have been made for a long time in the field of laminating, and after forming fine irregularities on the metal surface, Various techniques for obtaining adhesion by injection molding of a plastic resin have been studied.
  • JP 2001-225352 A discloses a method of chemically etching a metal surface in advance
  • JP 2003-103563 A discloses a method of treating a metal surface with a water-soluble reducing agent such as hydrazine
  • Japanese Patent Laid-Open No. 2006-1216 proposes to use an aluminum alloy finely processed by anodizing
  • Japanese Patent Laid-Open No. 2003-170531 discloses a metal surface-treated with an aqueous solution of a water-soluble amine compound. It has been proposed that an amorphous resin such as polycarbonate, polystyrene, ABS or the like is blended with a polybutylene terephthalate resin for injection molding and further obtaining bonding strength.
  • An object of the present invention is to provide a polybutylene terephthalate resin / metal composite molded body having sufficient adhesion strength and moldable at a mold temperature of 100 ° C. or lower.
  • a polybutylene terephthalate resin material containing a fibrous reinforcing agent and a thermoplastic elastomer as a polybutylene terephthalate resin material or a modified polyethylene containing a fibrous reinforcing agent.
  • the present invention relates to a polybutylene terephthalate resin composition containing a fibrous reinforcing agent and a thermoplastic elastomer, or a polybutylene terephthalate / isophthalic acid having an isophthalic acid component content of 3 to 50 mol% based on the total dicarboxylic acid component.
  • a modified polybutylene terephthalate resin composed of a copolymer and a modified polybutylene terephthalate resin composition containing a fibrous reinforcing agent and a metal (layer) whose surface has been subjected to fine unevenness are integrally attached. It is a composite molded body.
  • the polybutylene terephthalate resin material used in the present invention comprises (1) a polybutylene terephthalate resin composition containing a fibrous reinforcing agent and a thermoplastic elastomer, or (2) a content of isophthalic acid component is 3 with respect to the total dicarboxylic acid component.
  • a modified polybutylene terephthalate resin composition comprising a modified polybutylene terephthalate resin comprising a polybutylene terephthalate / isophthalic acid copolymer in an amount of ⁇ 50 mol% and a fibrous reinforcing agent.
  • the polybutylene terephthalate resin may be used alone as the polybutylene terephthalate resin, or the polybutylene terephthalate resin and the modified polybutylene terephthalate resin may be used in combination.
  • a modified polybutylene terephthalate resin and a polybutylene terephthalate resin may be used in combination.
  • the polybutylene terephthalate resin used in the present invention is polybutylene terephthalate obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and alkylene glycol having 4 carbon atoms or an ester-forming derivative thereof.
  • the polybutylene terephthalate may be a copolymer having 70% by weight or more.
  • Dibasic acid components other than terephthalic acid or its ester-forming derivatives include aliphatic, aromatic polybasic acids such as naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, succinic acid, or Examples of the glycol component other than 1,4-butanediol include ester alkylene derivatives such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane.
  • ester alkylene derivatives such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane.
  • Dimethanol lower alkylene glycol such as 1,3-octanediol, bisphenol A, aromatic alcohol such as 4,4′-dihydroxybiphenyl, ethylene oxide 2-mol adduct of bisphenol A, Scan phenol A alkylene oxide adduct alcohols, such as propylene oxide 3 mol adduct of glycerin, polyhydroxy compound or an ester-forming derivative thereof such as pentaerythritol, and the like.
  • aromatic alcohol such as 4,4′-dihydroxybiphenyl
  • any of the polybutylene terephthalates produced by polycondensation using the above compounds as monomer components can be used as the component (A) of the present invention, and are used alone or in admixture of two or more.
  • the branched polymer which belongs to a copolymer can also be used.
  • the polybutylene terephthalate branched polymer referred to here is a polyester mainly composed of so-called polybutylene terephthalate or butylene terephthalate monomer and branched by adding a polyfunctional compound.
  • polyfunctional compound examples include trimesic acid, trimellitic acid, pyromellitic acid and alcohol esters thereof, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
  • the modified polybutylene terephthalate resin referred to in the present invention is a polybutylene terephthalate / isophthalic acid copolymer in which the content of the isophthalic acid component is 3 to 50 mol% with respect to the total dicarboxylic acid component.
  • a polybutylene terephthalate / isophthalic acid copolymer is obtained by substituting terephthalic acid or a part of its ester-forming derivative portion with isophthalic acid in the polybutylene terephthalate.
  • a resin modified with 3 to 50 mol% with respect to the terephthalic acid component is generally used. If the modification ratio is less than 3 mol%, the elastomer component is not contained. Insufficient adhesion to metal is not obtained, and if the modification ratio exceeds 50 mol%, the solidification rate becomes slow and the productivity may be poor.
  • Isophthalic acid can be used for polycondensation in the form of a derivative capable of forming an ester, for example, a lower alcohol ester such as dimethyl ester, and can also be introduced as a copolymer component.
  • modification ratio is in the above range, a mixture of two or more polybutylene terephthalate / isophthalic acid copolymers having different diisophthalic acid contents can be used as the modified polybutylene terephthalate resin of the present invention.
  • the polybutylene terephthalate resin and the modified polybutylene terephthalate resin must be O-chlorophenol as a solvent and have an intrinsic viscosity (IV) measured at 35 ° C. in the range of 0.6 to 1.2 dl / g, preferably 0.65 to 1.0 dl / g, more preferably 0.65 to 0.8 dl / g. If the intrinsic viscosity is less than 0.6 dl / g, the amount of gas generated from polybutylene terephthalate resin such as tetrahydrofuran cannot be sufficiently reduced, and an appearance defect and deposit adhesion occur at the time of molding. On the other hand, if it exceeds 1.2 dl / g, the fluidity during molding becomes poor.
  • thermoplastic elastomer relieves strain and stress due to the difference between the linear expansion coefficient of the metal during molding and the shrinkage ratio of the resin, and the difference in linear expansion between the two materials after joining.
  • the polybutylene terephthalate resin which is engineering plastics, taking into consideration heat resistance, chemical resistance, etc.
  • a core-shell type elastomer, an olefin elastomer, and a polyester elastomer are preferable.
  • the blending amount of the thermoplastic elastomer is 3 to 100 parts by weight, preferably 10 to 50 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin.
  • the amount of the thermoplastic elastomer is less than 3 parts by weight, a sufficient effect on the adhesion between the metal and the resin cannot be obtained.
  • the amount of the thermoplastic elastomer is more than 100 parts by weight, the characteristics as a crystalline resin are reduced, and the polybutylene terephthalate resin composition As a result, the required performance such as heat resistance and chemical resistance may not be satisfied.
  • a core-shell type elastomer is an elastomer composed of a flexible core layer and a shell layer having a high elastic modulus.
  • the core layer contains 20 to 70% by weight of rubbery core polymer.
  • Such rubbery core polymers comprise at least one C 1 -C 8 alkyl acrylate monomer (methyl-, ethyl-, propyl, n-butyl, sec-butyl, tert-butyl, pentyl-, hexyl-, heptyl-, n-octyl and 2-ethylhexyl-acrylate), or C 1 -C 8 alkyl acrylate monomers different from at least one ethylenically unsaturated copolymer monomer and at least one cross-linking material Or a unit derived from a graft linker (eg, an unsaturated carboxylic acid allyl ester such as allyl methacrylate).
  • a graft linker
  • Acrylic core - shell layer of shell type elastomer is preferably shell polymer grafted to the core polymer, at least of the C 1 -C 8 alkyl methacrylate monomers derived from at least one C 1 -C 8 alkyl methacrylate monomers It contains 1 to 20% by weight, preferably 3 to 15% by weight, most preferably 4 to 8% by weight of units derived from at least one copolymerizable ethylenically unsaturated monomer different from one.
  • Suitable copolymerizable ethylenically unsaturated monomers include C 1 -C 8 alkyl (meth) acrylates, acrylonitrile, methacrylonitrile, divinylbenzene, alpha-methylstyrene, para-methylstyrene, chlorostyrene, vinyltoluene, dibromo.
  • C 9 -C which has a larger carbon number such as styrene, tribromostyrene, vinyl naphthalene, isopropenyl naphthalene and, for example, decyl acrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, isobornyl methacrylate 20 alkyl (meth) acrylate etc. are mentioned.
  • C 1 -C 8 alkyl (meth) acrylate monomers are preferred because of their improved weather resistance, and most preferred are C 1 -C 8 alkyl acrylate monomers.
  • polyolefin elastomer examples include those having a polyolefin as a main chain and a vinyl polymer as a side chain and grafted with styrene or an acrylonitrile-styrene copolymer.
  • Polyolefins used as the main chain include ethylene, propylene, isoprene, fatty acid vinyl esters (vinyl acetate, vinyl propionate, etc.), acrylic esters (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.) Acrylic acid C 1 -C 10 alkyl ester and the like) and the like.
  • Examples of such olefinic main chain include ethylene-vinyl acetate copolymer, ethylene-acrylic acid C 1 -C 8 alkyl ester copolymer (ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic). Acid butyl copolymer, etc.), ethylene-acrylic acid C 1 -C 8 alkyl ester- (meth) acrylic acid copolymer, ethylene-styrene copolymer and the like.
  • polyester elastomer a copolymer containing a hard segment made of a short chain ester, a polyether component having a number average molecular weight of about 200 to 6000, and a soft segment made of a polyester component having a number average molecular weight of about 200 to 10000
  • the ratio of the hard segment to the soft segment is 20 to 90 (% by weight) to 80 to 10 (% by weight), preferably 30 to 85 (% by weight) to 70 to 15 (% by weight).
  • dicarboxylic acid component constituting the polyester hard segment terephthalic acid and isophthalic acid are preferable.
  • the diol component constituting the polyester hard segment includes aliphatic or alicyclic diols having 2 to 12 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-butenediol, neopentyl.
  • Bisphenols such as glycol, 1,5-pentanediol, 1,6-hexanediol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) methane, bis (p-hydroxyphenyl) propane, and mixtures thereof preferable.
  • the polyether component constituting the soft segment is particularly preferably poly (alkylene oxide) glycol, and particularly preferably poly (tetramethylene oxide) glycol.
  • the polyester component constituting the soft segment is an aliphatic hydrocarbon having 2 to 12 carbon atoms, and is preferably a polycondensate of a compound having a carboxylic acid and an alcohol terminal in the same molecule, or a ring-opening polymer of a cyclic ester. And caprolactone polymers are preferred.
  • thermoplastic resin elastomers a core-shell type elastomer and an olefin-based elastomer are particularly preferably used in a use environment that requires hydrolysis resistance and heat aging resistance.
  • the resin composition used in the present invention is blended with a fibrous reinforcing agent in order to improve mechanical strength such as tensile strength, to suppress the shrinkage rate of the molded product and to improve the adhesion to the metal.
  • fibrous reinforcing agent examples include inorganic fibers [for example, glass fibers, carbon fibers, silica / alumina fibers, zirconia fibers, metal fibers (for example, stainless steel, aluminum, titanium, copper, brass, etc.)], organic fibers ( For example, aromatic polyamide fiber, fluororesin fiber, liquid crystalline aromatic fiber, etc.) are included and used alone or in combination of two or more. Glass fiber is preferably used from the standpoint of availability and cost.
  • inorganic fibers for example, glass fibers, carbon fibers, silica / alumina fibers, zirconia fibers, metal fibers (for example, stainless steel, aluminum, titanium, copper, brass, etc.)
  • organic fibers for example, aromatic polyamide fiber, fluororesin fiber, liquid crystalline aromatic fiber, etc.
  • Glass fiber is preferably used from the standpoint of availability and cost.
  • the average fiber diameter of the fibrous reinforcing agent is not particularly limited, and is, for example, 1 to 100 ⁇ m (for example, 1 to 50 ⁇ m), preferably about 3 to 30 ⁇ m.
  • the average fiber length of the fibrous reinforcing agent is not particularly limited and is, for example, about 0.1 to 20 mm.
  • the fibrous reinforcing agent one having a circular cross section is usually used, but a modified cross-section glass may be used from the viewpoint of suppressing warping deformation of the molded product and preventing a decrease in adhesion after molding.
  • the fibrous reinforcing agent may be surface-treated with a sizing agent or a surface treatment agent (for example, a functional compound such as an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, a titanate compound) as necessary. Good.
  • the fibrous reinforcing agent may be surface-treated in advance with the sizing agent or the surface treatment agent, or may be surface-treated by adding the sizing agent or the surface treatment agent when preparing the material.
  • the compounding amount of the fibrous reinforcing agent is 20 to 100 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin and / or the modified polybutylene terephthalate resin. If the blending amount is less than 20 parts by weight, the adhesion with the metal may be lowered, and the mechanical properties are insufficient. If it exceeds 100 parts by weight, the melt-kneading property is deteriorated and the moldability is lowered.
  • an inorganic filler other than the fibrous reinforcing agent can be added.
  • silicates such as mica, talc and bentonite, calcium carbonate, magnesium hydroxide, boehmite, zinc sulfate, zinc oxide, glass flakes and glass beads can be used alone or in combination. If the amount is appropriate, the difference between the resin and the metal related to shrinkage and linear expansion can be alleviated.
  • additives for example, antioxidants, ultraviolet absorbers, heat stabilizers, stabilizers such as weather stabilizers, lubricants, mold release agents, Coloring or the like may be added.
  • the resin composition used in the present invention has other thermoplastic resins (for example, polyamide, acrylate, polycarbonate, polyarylate, polylactic acid, polystyrene, polyphenylene as long as the performance as a polybutylene terephthalate resin is not lowered.
  • thermoplastic resins for example, polyamide, acrylate, polycarbonate, polyarylate, polylactic acid, polystyrene, polyphenylene
  • thermosetting resins for example, unsaturated polybutylene terephthalate resin, phenol resin, epoxy resin, etc.
  • the polybutylene terephthalate resin composition used in the present invention may be a powder mixture or a molten mixture, and can be prepared by mixing inorganic fillers, additives, and the like, if necessary, by conventional methods.
  • each component can be mixed, kneaded by a single or twin screw extruder, extruded, and pelletized.
  • a composite molded body can be obtained by injection molding using the polybutylene terephthalate resin composition thus prepared and a metal whose surface has been subjected to fine unevenness treatment.
  • the polybutylene terephthalate resin composition used in the present invention can obtain good adhesion even when it is molded at a mold temperature of 100 ° C. or less, which is a range of a normal water temperature controller. There is no need to raise the mold temperature more than necessary.
  • the metal surface treatment method used in the present invention is not particularly limited, and any method can be selected as desired according to the metal material, shape, required characteristics, and the like.
  • Examples of the fine uneven treatment on the metal surface include chemical etching, anodizing treatment on aluminum, physical treatment such as liquid honing and sand blasting, and processing by electroless plating.
  • chemical etching there are various methods for treating a metal surface with a synthetic chemical or the like depending on the type of metal and the purpose of treatment, and it is used in various industrial fields today.
  • Specific examples of etching include methods described in, for example, JP-A-10-96088 and JP-A-10-56263, and there is no particular limitation, and any conventional method can be selected.
  • Alumite treatment is a general surface treatment method applied to aluminum, and an aluminum is electrolyzed with an anode using an acid to form a porous material on the order of several tens of nanometers to several tens of micrometers. Is possible. Further, not only forming a concave portion on the surface, but conversely, TRI treatment or the like is known as a method for forming a convex portion.
  • the fine unevenness processing of the metal surface is to form unevenness of several tens nm to several tens ⁇ m size by using a chemical, physical, electrical method, or a combination thereof.
  • the effect of the present invention can be obtained.
  • the uneven diameter is finer, it becomes difficult to confirm, and it becomes difficult to enter the resin during molding. Moreover, since it will become too large, since the contact area with resin will reduce, it becomes difficult to obtain the target joint strength.
  • the metal species used in the present invention is not particularly limited, and for example, copper, aluminum, magnesium, nickel, titanium, iron, etc. and alloys thereof can be used. Moreover, it can utilize similarly about the metal in the metal surface plated by nickel, chromium, gold
  • FIG. 1 is a diagram showing the shape of a composite molded product for measuring adhesion strength.
  • FIG. 2 is a diagram illustrating a situation in which the adhesion strength of the composite molded product is measured.
  • FIG. 3 is a diagram showing the shape of the composite molded product used in the airtightness test.
  • FIG. 4 is a diagram showing a situation of an airtightness test of the composite molded product.
  • the part in an Example shows a weight part.
  • Examples 1 to 7 Comparative Examples 1 to 3
  • the polybutylene terephthalate resin composition having the composition shown in Table 1 was prepared by compounding at a cylinder temperature of 260 ° C. using a twin screw extruder manufactured by Nippon Steel Co., Ltd.
  • a composite molded article for measuring adhesion strength shown in FIG. 1 was molded from the obtained resin composition using an injection molding machine manufactured by Sodec.
  • As the metal aluminum (A1050) subjected to “NMT treatment by Taisei Plus Co., Ltd.” known as a kind of chemical etching was used. Molding was performed under two conditions of a mold temperature of 90 ° C and 140 ° C. With respect to the adhesion strength, as shown in FIG. 2, the fracture strength was measured by pressing the protruding portion against a jig at a constant speed using the composite molded product shown in FIG. For the measurement, Tensilon UTA-50KN-RTC manufactured by Orientec was used. As shown in Table 1, although high adhesion was obtained at a mold temperature of 140 ° C., only those of Examples showed high adhesion at a mold temperature of 90 ° C.
  • a composite molded product shown in FIG. 3 was obtained by insert-molding an aluminum pin that was similarly surface-treated at a mold temperature of 90 ° C., and this was set in a jig shown in FIG. Evaluation was performed by applying pressure with compressed air and confirming airtight leakage from the interface between the metal and the resin. The pressure was held for 1 minute in increments of 0.1 MPa, and when no airtight leakage could be confirmed, the pressure was further increased by 0.1 MPa and the measurement was performed up to a maximum of 0.6 MPa. The results are shown in Table 1.
  • Polybutylene terephthalate resin Polybutylene terephthalate resin (manufactured by Wintech Polymer) with an intrinsic viscosity of 0.7 dl / g
  • Polybutylene terephthalate / isophthalic acid copolymer Polybutylene terephthalate copolymer in which 12.5 mol% of terephthalic acid in the polybutylene terephthalate skeleton is modified with isophthalic acid (inherent viscosity 0.74dl / g, manufactured by Wintech Polymer)
  • b Core-shell type elastomer (Rohm & Haas Paraloid EXL-2311)
  • c Olefin-based elastomer (Nippon Yushi Co., Ltd. Modiper A5300)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un corps moulé composite métal/résine polybutylène téréphtalate qui présente une résistance à l'adhérence suffisante et peut être moulé à une température de moulage ne dépassant pas 100˚C. L'invention concerne spécifiquement un corps moulé composite dans lequel une composition de résine polybutylène téréphtalate ou une composition de résine polybutylène téréphtalate modifiée, et un métal (couche) ayant une surface soumise à un traitement de rugosification fine sont intégralement liés l'un à l'autre. La composition de résine polybutylène téréphtalate contient un agent de renforcement fibreux et un élastomère thermoplastique, tandis que la composition de résine polybutylène téréphtalate modifiée contient une résine polybutylène téréphtalate modifiée, qui est composée d'un copolymère polybutylène téréphtalate/acide isophtalique contenant entre 3 et 50 % par mole d'un composant d'acide isophtalique par rapport au total des composants d'acide dicarboxylique, et d'un agent de renforcement fibreux.
PCT/JP2008/003826 2007-12-21 2008-12-18 Corps moulé composite WO2009081549A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/746,617 US20100261025A1 (en) 2007-12-21 2008-12-18 Composite molded product
CN2008801215376A CN101903170A (zh) 2007-12-21 2008-12-18 复合成形体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007330133A JP5242150B2 (ja) 2007-12-21 2007-12-21 複合成形体
JP2007-330133 2007-12-21

Publications (1)

Publication Number Publication Date
WO2009081549A1 true WO2009081549A1 (fr) 2009-07-02

Family

ID=40800867

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/003826 WO2009081549A1 (fr) 2007-12-21 2008-12-18 Corps moulé composite

Country Status (5)

Country Link
US (1) US20100261025A1 (fr)
JP (1) JP5242150B2 (fr)
KR (1) KR20100094523A (fr)
CN (1) CN101903170A (fr)
WO (1) WO2009081549A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180098266A (ko) 2015-12-28 2018-09-03 윈테크 폴리머 가부시키가이샤 폴리부틸렌테레프탈레이트 수지 조성물, 및 금속 복합 부품

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6446262A (en) * 1987-08-12 1989-02-20 Victor Company Of Japan System for recording disk inspection signal and inspection signal recording disk
CN102933656B (zh) * 2010-06-09 2014-10-29 胜技高分子株式会社 聚对苯二甲酸丁二醇酯树脂组合物、金属复合部件、及金属复合部件的制造方法
MY160890A (en) 2010-06-10 2017-03-31 Wintech Polymer Ltd Modified polyalkylene terephthalate resin for improving adhesion, modified polyalkylene terephthalate resin composition for improving adhesion, resin molded article, and bonded article
JP5555146B2 (ja) * 2010-12-01 2014-07-23 株式会社日立製作所 金属樹脂複合構造体及びその製造方法、並びにバスバ、モジュールケース及び樹脂製コネクタ部品
JP6183082B2 (ja) * 2012-09-13 2017-08-23 東洋紡株式会社 金属被覆用樹脂組成物
JP5717928B2 (ja) 2012-09-21 2015-05-13 帝人株式会社 複合材料の製造方法
JP6276080B2 (ja) * 2014-03-25 2018-02-07 ダイセルポリマー株式会社 繊維強化熱可塑性樹脂組成物、それを使用した複合成形体とその製造方法
US9574069B2 (en) * 2014-04-30 2017-02-21 Lehigh Technologies, Inc. Chemically functionalized renewed rubber composition
JP6231460B2 (ja) * 2014-10-30 2017-11-15 株式会社神戸製鋼所 金属・樹脂複合材料
JP6332248B2 (ja) * 2015-11-30 2018-05-30 トヨタ自動車株式会社 樹脂体及び樹脂体の製造方法
BR112018015159B1 (pt) * 2016-02-17 2022-03-08 The University Of Tokyo Método de produção para membro de compósito, e membro de compósito
JP6902841B2 (ja) * 2016-10-03 2021-07-14 三菱エンジニアリングプラスチックス株式会社 金属樹脂複合体及びその製造方法
JP7278529B2 (ja) * 2017-02-28 2023-05-22 東洋紡エムシー株式会社 ポリエステルエラストマーを溶着する成形体用ポリブチレンテレフタレート樹脂組成物および複合成形体
JP7074055B2 (ja) 2017-02-28 2022-05-24 東洋紡株式会社 ポリエステルエラストマーを溶着する成形体用ポリブチレンテレフタレート樹脂組成物および複合成形体
WO2019047832A1 (fr) * 2017-09-08 2019-03-14 东丽先端材料研究开发（中国）有限公司 Corps lié de composition de résine thermoplastique et métal et leur procédé de fabrication
EP3674368B1 (fr) * 2017-10-03 2023-12-06 Mitsubishi Engineering-Plastics Corporation Corps composite en résine métallique, composition de résine et procédé de production de corps composite en résine métallique
JP7202308B2 (ja) 2017-10-03 2023-01-11 三菱エンジニアリングプラスチックス株式会社 金属樹脂複合体および金属樹脂複合体の製造方法
WO2019087961A1 (fr) 2017-10-30 2019-05-09 株式会社クラレ Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
KR102546851B1 (ko) * 2018-06-29 2023-06-23 이데미쓰 고산 가부시키가이샤 수지 금속 복합체 및 그의 제조 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003103563A (ja) * 2001-07-25 2003-04-09 Taisei Plas Co Ltd 金属と樹脂の複合体とその製造方法
JP2004050488A (ja) * 2002-07-17 2004-02-19 Taisei Plas Co Ltd アルミニューム合金と樹脂の複合体とその製造方法
JP2007175873A (ja) * 2005-12-26 2007-07-12 Taisei Plas Co Ltd アルミニウム合金と樹脂の複合体とその製造方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3619081A1 (de) * 1986-06-06 1987-12-10 Bayer Ag Spritzgusskoerper und verfahren zu seiner herstellung
JPH0721103B2 (ja) * 1988-03-02 1995-03-08 ポリプラスチックス株式会社 難燃性ポリブチレンテレフタレート樹脂組成物及び電気部品用成形品
JPH09262863A (ja) * 1996-03-28 1997-10-07 Polyplastics Co インサート成形品
JP3338330B2 (ja) * 1997-05-09 2002-10-28 帝人株式会社 ポリエステル樹脂複合成形品
DE19820399A1 (de) * 1998-05-07 1999-11-11 Basf Ag Flammgeschützte Polyesterformmassen
US6447913B1 (en) * 1999-06-23 2002-09-10 Polyplastics Co., Ltd Thermoplastic polyester resin composition
JP2001225346A (ja) * 1999-12-08 2001-08-21 Polyplastics Co 金属インサート樹脂複合成形品の製造方法
JP2001181489A (ja) * 1999-12-27 2001-07-03 Polyplastics Co ポリエステル樹脂組成物
JP4205283B2 (ja) * 2000-03-08 2009-01-07 帝人株式会社 コネクター用樹脂ペレット混合物およびその製造方法
JP3876141B2 (ja) * 2001-03-28 2007-01-31 東レ株式会社 ポリエステル系樹脂組成物およびその成形品
WO2004029154A1 (fr) * 2002-09-25 2004-04-08 Toray Industries, Inc. Composition de resine de polybutylene terephtalate retardateur de flamme, et pieces moulees y relatives
JP4112378B2 (ja) * 2003-01-10 2008-07-02 大成プラス株式会社 金属と熱可塑性樹脂組成物の複合体とその製造方法
ATE417078T1 (de) * 2003-05-02 2008-12-15 Toray Industries Polyesterharzzusammensetzung
CN1882428B (zh) * 2003-11-14 2010-10-06 小仓离合机株式会社 树脂涂布方法和镶嵌模塑品及树脂涂覆金属齿轮类
JP2006104363A (ja) * 2004-10-07 2006-04-20 Wintech Polymer Ltd ポリブチレンテレフタレート樹脂組成物
JP4799857B2 (ja) * 2004-12-24 2011-10-26 ウィンテックポリマー株式会社 インサート成形品
JP5057422B2 (ja) * 2005-03-31 2012-10-24 日本ケミコン株式会社 コンデンサ
US8703272B2 (en) * 2005-10-04 2014-04-22 Taisei Plas Co., Ltd. Composite of metal and resin and method for manufacturing same
JP5124129B2 (ja) * 2005-12-08 2013-01-23 東レ株式会社 アルミニウム合金と樹脂の複合体及びその製造方法
EP1979403B1 (fr) * 2006-01-27 2009-12-30 General Electric Company Articles derives de compositions contenant des copolymeres aleatoires de polybutylene terephtalate (pbt) modifie derives de polyethylene terephtalate (pet)
EP1994072A2 (fr) * 2006-01-27 2008-11-26 General Electric Company Compositions de moulage contenant des polyalkylene terephtalates et descopolymeres aleatoires de polybutylene terephtalate (pbt) modifie derives de pet
JP2007203585A (ja) * 2006-02-01 2007-08-16 Taisei Plas Co Ltd アルミニウム合金と樹脂の複合体とその製造方法
JP5312783B2 (ja) * 2007-12-26 2013-10-09 ウィンテックポリマー株式会社 ポリブチレンテレフタレート樹脂組成物
JP5351415B2 (ja) * 2007-12-26 2013-11-27 ウィンテックポリマー株式会社 ポリブチレンテレフタレート樹脂組成物
WO2009150833A1 (fr) * 2008-06-11 2009-12-17 ウィンテックポリマー株式会社 Composition de résine polytéréphtalate de butylène et son moulage
CN102056724A (zh) * 2008-06-12 2011-05-11 日本轻金属株式会社 铝-树脂注塑一体成形品及其制造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003103563A (ja) * 2001-07-25 2003-04-09 Taisei Plas Co Ltd 金属と樹脂の複合体とその製造方法
JP2004050488A (ja) * 2002-07-17 2004-02-19 Taisei Plas Co Ltd アルミニューム合金と樹脂の複合体とその製造方法
JP2007175873A (ja) * 2005-12-26 2007-07-12 Taisei Plas Co Ltd アルミニウム合金と樹脂の複合体とその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180098266A (ko) 2015-12-28 2018-09-03 윈테크 폴리머 가부시키가이샤 폴리부틸렌테레프탈레이트 수지 조성물, 및 금속 복합 부품

Also Published As

Publication number Publication date
US20100261025A1 (en) 2010-10-14
CN101903170A (zh) 2010-12-01
JP5242150B2 (ja) 2013-07-24
KR20100094523A (ko) 2010-08-26
JP2009149018A (ja) 2009-07-09

Similar Documents

Publication Publication Date Title
JP5242150B2 (ja) 複合成形体
JP6668174B2 (ja) 樹脂金属複合体及びその製造方法
JP6655537B2 (ja) 熱可塑性樹脂組成物およびその成形体
JP5581606B2 (ja) 成形性の優れた樹脂組成物、及びその成形体
JP2010001363A (ja) 熱可塑性エラストマ樹脂組成物および成形体
WO2008075776A1 (fr) Composition de résine de téréphtalate de polybutylène
KR20210001616A (ko) 열가소성 수지 조성물 및 이를 이용한 성형품
KR102018712B1 (ko) 열가소성 수지 조성물 및 이를 이용한 성형품
JP6749174B2 (ja) レーザーダイレクトストラクチャリング用ポリエステル系樹脂組成物
JP2013082942A (ja) ポリエステル樹脂組成物及びこれを成形してなる樹脂製基体
JP6902841B2 (ja) 金属樹脂複合体及びその製造方法
JP5360713B2 (ja) 熱可塑性エラストマ樹脂組成物および成形体
KR102001484B1 (ko) 열가소성 수지 조성물 및 이를 이용한 성형품
JP6506806B2 (ja) ポリブチレンテレフタレート樹脂組成物、成形品及び複合体
JP4657670B2 (ja) ポリブチレンテレフタレート樹脂組成物
JP2006169460A (ja) 熱可塑性樹脂組成物およびそれからなる成形品
JP2006206921A (ja) ポリエステル樹脂組成物よりなる自動車用部品
WO2016104201A1 (fr) Composition de résine de poly(téréphtalate d'alkylène)
JP2005240003A (ja) 熱可塑性ポリエステル樹脂組成物及びインサート成形品
JP6163862B2 (ja) 熱可塑性樹脂組成物およびその製造方法
JP5408853B2 (ja) ポリエステル樹脂組成物及びこれを成形してなる樹脂製基体
JP4785398B2 (ja) 射出圧縮成形法
JP7193382B2 (ja) 係合部を有するポリアルキレンテレフタレート樹脂成形品
JP2024058068A (ja) 薄肉複合成形体用熱可塑性ポリエステルエラストマー樹脂組成物
JP2001181491A (ja) 難燃性ポリエステル樹脂組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880121537.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08865584

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 12746617

Country of ref document: US

ENP Entry into the national phase

Ref document number: 20107013581

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08865584

Country of ref document: EP

Kind code of ref document: A1